EP2300146B1 - Process for preparing polyurea microcapsules - Google Patents
Process for preparing polyurea microcapsules Download PDFInfo
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- EP2300146B1 EP2300146B1 EP09766232.4A EP09766232A EP2300146B1 EP 2300146 B1 EP2300146 B1 EP 2300146B1 EP 09766232 A EP09766232 A EP 09766232A EP 2300146 B1 EP2300146 B1 EP 2300146B1
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- perfume
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
- B01J13/06—Making microcapsules or microballoons by phase separation
- B01J13/14—Polymerisation; cross-linking
- B01J13/16—Interfacial polymerisation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
- B01J13/20—After-treatment of capsule walls, e.g. hardening
- B01J13/22—Coating
Definitions
- the present invention relates to a process for producing perfume-containing microcapsules with a polyurea wall that can be used in home or personal care products, as well as to the microcapsules themselves and consumer products comprising these microcapsules.
- the process of the invention uses a particular colloidal stabilizer in the form of an aqueous solution comprising defined proportions of particular polymers.
- Polyurea capsules formed by polymerisation between a polyisocanate and a polyamine, are well known in the art.
- delivery systems may suffer from stability problems, in particular when incorporated into surfactant based products such as detergents, which are strongly aggressive towards said delivery systems.
- WO 01/41915 discloses a process for the preparation of capsules carrying cationic charges. Such a process is allegedly applicable to a large variety of microcapsules, in particular polyurethane-polyurea microcapsules are mentioned.
- the capsules are placed in a medium which is favourable for the treatment with cationic polymers.
- the treatment with cationic polymers is carried out after purification of the basic capsule slurry, in order to eliminate anionic or neutral polymers which were not incorporated in the capsule wall during formation thereof, and other free electrically charged compounds involved in the encapsulation process.
- the capsules are diluted, isolated and then resuspended in water, or even washed to further eliminate anionic compounds.
- the capsules are agitated vigorously and the cationic polymers are added.
- Partially quaternized copolymers of polyvinylpyrrolidones are cited to this purpose, among many other suitable polymers.
- the described process comprises several steps following the capsule formation, said process being therefore time consuming and not economically profitable.
- US 2006/0216509 also discloses a process for the cationization of polyurea capsules. This process involves the addition, during the wall formation, of polyamines, the capsules thus bearing latent charges, depending on the pH of the medium. Once formed, the capsules are subsequently cationized by acid action or alkylation to bear permanent positive charges. The cationic compounds therefore react with the capsule wall, chemically changing the latter.
- polyurea microcapsules are not cationic.
- US 5,225,118 discloses polyurea microcapsules comprising a colloidal stabilizer in the form of an aqueous solution of polyvinyl alcohol and polyvinyl pyrrolidone but this stabilizer is not cationic and thus the microcapsules do not bear any positive charge.
- the microcapsules of the invention show a better deposition on the surface on which they are applied and further show a better dispersion in product bases.
- microcapsules of the invention have the surprising and advantageous effect of being better dispersed in product bases, especially in unstructured liquid detergents.
- the present invention provides a new simplified process for the preparation of polyurea microcapsules. It advantageously solves the problem of providing a single-step process for preparing polyurea microcapsules bearing permanent positive charges, the capsules being stable, well dispersed in product bases and well deposited on the substrate on which the perfumed product is applied.
- a single-step process we mean a process that does not involve any further step, after the capsule formation, unlike what is the case in the prior art.
- the present invention relates to a process for preparing cationic polyurea microcapsules encapsulating a perfume.
- the invention concerns the capsules themselves as well as perfuming compositions and perfumed articles containing them.
- One object of the present invention is a process for the preparation of polyurea microcapsules comprising
- the perfume in which the polyisocyanate is dissolved in step a) can be a perfuming ingredient alone or a mixture of ingredients, in the form of a perfuming composition.
- perfuming ingredients may be found in the current literature, for example in Perfume and Flavour Chemicals, 1969 (and later editions), by S. Arctander, Montclair N.J. (USA ), as well as in the vast patent and other literature related to the perfume industry. They are well known to the skilled person in the art of perfuming consumer products, that is, of imparting a pleasant odour to a consumer product.
- the perfuming ingredients may be dissolved in a solvent of current use in the perfume industry.
- the solvent is preferably not an alcohol.
- solvents are diethyl phthalate, isopropyl myristate, Abalyn ® , benzyl benzoate, ethyl citrate, limonene or other terpenes, or isoparaffins.
- the solvent is very hydrophobic and highly sterically hindered, like for example Abalyn ® .
- the perfume comprises less than 30% of solvent. More preferably the perfume comprises less than 20% and even more preferably less than 10% of solvent, all these percentages being defined by weight relative to the total weight of the perfume. Most preferably, the perfume is essentially free of solvent.
- Preferred ingredients are those having a high steric hindrance and in particular those from one of the following groups:
- the perfume in which the polyisocyanate is dissolved comprises at least 30%, preferably at least 50%, more preferably at least 60% of ingredients selected from Groups 1 to 7, as defined above. More preferably said perfuming composition comprises at least 30%, preferably at least 50% of ingredients from Groups 3 to 7, as defined above. Most preferably said composition comprises at least 30%, preferably at least 50% of ingredients from Groups 3, 4, 6 or 7, as defined above.
- the perfume comprises at least 30%, preferably at least 50%, more preferably at least 60% of ingredients having a logP above 3, preferably above 3.5 and even more preferably above 3.75.
- the perfume used in the process of the invention contains less than 5% of its own weight of primary alcohols, less than 10% of its own weight of secondary alcohols and less than 15% of its own weight of tertiary alcohols.
- the perfume used in the process of the invention does not contain any primary alcohols and contains less than 10% of secondary and tertiary alcohols.
- an amount of between 28 and 60% of perfume in the process of the invention there is used an amount of between 28 and 60% of perfume in the process of the invention, these percentages being defined by weight relative to the total weight of the microcapsules.
- the polyisocyanate used in the process of the invention comprises at least two isocyanate groups. Preferably it contains at least three isocyanate groups. Following these numbers of functional groups, an optimal reticulation or network of the capsules wall is achieved, providing thus microcapsules exhibiting a surprising prolonged slow release of fragrances, as well as a surprising improved stability in the consumer product.
- the polyisocyanate is preferably selected from the group consisting of a trimer of hexamethylene diisocyanate, a trimer of isophorone diisocyanate or a Biuret of hexamethylene diisocyanate, among which a Biuret of hexamethylene diisocyanate is even more preferred.
- the polyisocyanate is added in an amount comprised between 2 and 20% by weight, relative to the total weight of the solution.
- the colloidal stabilizer added in step b) comprises polyvinyl alcohol as stabilizer and a cationic copolymer of vinylpyrrolidone and of a quaternized vinylimidazol, which is very efficient in dispersing the capsules in surfactant-based consumer products.
- the colloidal stabilizer is in the form of an aqueous solution of
- polymers must be added in the concentrations defined above in order to obtain a stable emulsion, which does not phase separate.
- using higher concentrations of polyvinyl alcohol induces a phase separation when the capsules are added to a surfactant-based consumer product.
- the colloidal stabilizer is easily prepared by dissolving both polymers in water.
- the cationic copolymer of vinylpyrrolidone and of a quaternized vinylimidazol is one of those sold under the trade name Luviquat ® , in particular Luviquat ® Ultra Care or Luviquat ® FC 550 (origin BASF), these product being defined as copolymers of vinylpyrrolidone (VP) and quaternized vinylimidazol (QVI) with a range of charge densities, in aqueous solution.
- step c) of the process of the invention a reactant selected from the group of water soluble guanidine salts and guanidine is added.
- water soluble guanidine salt it is meant a salt soluble in water and resulting from the reaction of guanidine with an acid.
- guanidine carbonate is one example of such salts.
- the polyurea wall of the microcapsules is the result of the interfacial polymerisation between the polyisocyanate dissolved in step a) and the reactant added in step c).
- step c for each mole of isocyanate group dissolved in the perfume in step a), 1 to 3, preferably 1.2 to 2 moles of guanidine or guanidine salt are added in step c). Accordingly there is added an excess of said reactant.
- the reaction starts immediately after adding said reactant. Preferably the reaction is maintained for 2 to 15 hours, more preferably for 4 to 10 hours.
- the specific composition of the polyurea wall is key in obtaining microcapsules that are at the fine balance between release and retention so as to achieve satisfactory slow and constant release of fragrances over time, once the capsules are placed on textiles or hair, while showing the desired stability in the product base (e.g. counteracts efficiently the extraction of the perfume by the surfactants of the consumer product). Therefore the selection of the guanidine or guanidine salt and of the polyisocyanate, among the ones mentioned above, enables the fine tuning of the properties and stability of the capsules.
- the dispersion may be prepared by high shear mixing and adjusted to the desired droplet size. Droplet size may be checked with light scattering measurements or microscopy.
- a dispersion is characterized by the stabilization of the oil droplets by a colloidal stabilizer, in contrast to an emulsion, wherein the oil droplets are stabilized by emulsifiers.
- microcapsules obtained by the process of any of the above-described embodiments are also one object of the present invention. Therefore, microcapsules comprising
- microcapsules obtained have a mean diameter comprised between 1 and 50 ⁇ m and preferably comprised between 5 and 20 ⁇ m.
- mean diameter refers to the arithmetic mean. The present inventors found that with microcapsules of this size, optimal deposition and/or adherence of microcapsules to the targeted surface, e.g. textile, hair or skin, is obtained.
- microcapsules are also preferably characterised by a Zeta potential comprised between 20 and 60 mV, preferably between 25 and 45 mV.
- the polyurea wall composition, the polyisocyanate, the perfume, the colloidal stabilizer and the guanidine or the water-soluble guanidine salt are as defined above, in relation to the process of preparation of the microcapsules.
- microcapsules of the invention can be advantageously used for the controlled release of the encapsulated perfume. It is therefore particularly appreciated to include these microcapsules as perfuming ingredients in a perfumed consumer product. This result is highly surprising since said consumer products may contain high amounts (typically more than 10% of their own weight) of specific types of surfactant/tensioactive/solvents and which are known to significantly diminish the stability and the performance of said capsules. In other words, the use of the invention's microcapsules in the consumer products provides unexpected advantages over the same use of other similar prior art capsules.
- the cationic polyurea microcapsules obtained by the process of the invention provide improved deposition of the perfume on the treated surface together with an improved stability in a chemically aggressive environment and thus a good retention of the perfume, especially in detergents and fabric softeners.
- the cationic polyurea microcapsules are also well dispersed in the consumer product bases, so that no phase separation is induced upon addition of the capsules to the base and during a sufficient storage period.
- the microcapsules of the invention provide a controlled release of the encapsulated perfume, said perfume being slowly released from the microcapsules, thus considerably improving the perfume long-lastingness and intensity.
- a perfumed consumer product comprising the microcapsules of the invention are therefore also objects of the present invention.
- the consumer product may be in the form of a home- or personal-care product.
- it is in the form of a liquid shampoo, hair conditioner, shower gel, detergent, all-purpose cleaner or fabric softener or in the form of a powder or tablet detergent.
- the consumer product is in the form of a liquid, powder or tablet detergent, or in the form of a fabric softener.
- detergents we include here products such as detergent compositions or cleaning products for washing up or for cleaning various surfaces, for example intended for the treatment of textiles, dishes or hard surfaces (floors, tiles, stone-floors, etc).
- the surface is a textile.
- the reaction mixture obtained in the process of the invention may be used as such to perfume the consumer products.
- the reaction mixture may be directly added to a liquid fabric softener at a rate of 0.1 to 30% by weight relative to the total weight of the softener.
- the microcapsules obtained in the process of the invention may be isolated from the reaction mixture before being incorporated into a consumer product.
- the reaction mixture comprising the microcapsules of the invention may be sprayed onto a dry, powdered product, such as a washing powder or powdered detergent or the microcapsules may be dried and added to these products in solid form.
- the consumer product comprises from 0.01 to 4.5%, more preferably from 0.01 to 4% of the microcapsules of the present invention, these percentages being defined by weight relative to the total weight of the consumer product.
- concentrations may be adapted according to the olfactive effect desired in each product.
- Formulations of consumer product bases in which the microcapsules of the invention can be incorporated can be found in the abundant literature relative to such products. These formulations do not warrant a detailed description here, which would in any case not be exhaustive. The person skilled in the art of formulating such consumer products is perfectly able to select the suitable components on the basis of his general knowledge and of the available literature.
- Polyurea capsules were prepared in a one litre glass double-jacketed reactor equipped with a scrapped stirrer and with an Ystral-rotor/stator system (500-1800 rpm).
- the aqueous stabilizer solution was prepared by dissolving the polyvinyl alcohol (Mowiol ® 18-88, origin: Fluka) and the cationic copolymer Luviquat ® Ultra Care (polyquaternium-44, origin: BASF) in deionised water.
- the final concentration of the polyvinyl alcohol was 0.25% while the concentration of Luviquat ® Ultra Care was 0.75%, these percentages being relative to the total weight of the stabilizer solution.
- the stabilizer solution was introduced into the reactor at room temperature in an amount of 582.50 g.
- the scrapped stirrer was stopped and then a pre-emulsion was prepared by dispersing the perfume phase in the aqueous phase with the rotor/stator system. During this step, the temperature was maintained at 10°C. The time and the speed of stirring were adjusted to reach the desired size distribution of the emulsion. Once the emulsion was prepared, the stirring was continued with the scrapped stirrer at 200 rpm till the end of the process.
- the perfume content in the capsules suspension was around 28%, relative to the total weight of the suspension.
- the size distribution of the capsules was controlled by Optical Microscopy and Light Scattering (Mastersizer S, Malvern) while the surface charge was controlled by Zeta potential measurements (Nanosizer, Malvern).
- the synthesis was repeated several times and the value of the Zeta potential measured for the obtained capsules were comprised between +8 and +20 mV, thus indicating that the capsules were cationically charged.
- Polyurea capsules were prepared in a one litre glass double-jacketed reactor equipped with a scrapped stirrer and with an Ystral-rotor/stator system (500-1800 rpm).
- the aqueous stabilizer solution was prepared by dissolving the polyvinyl alcohol (Mowiol ® 18-88, origin: Fluka) and the cationic copolymer Luviquat ® Ultra Care (polyquaternium-44, origin: BASF) in deionised water.
- the final concentration of the polyvinyl alcohol was 0.25% while the concentration of Luviquat ® Ultra Care was 0.75%, these percentages being relative to the total weight of the stabilizer solution.
- the stabilizer solution was introduced in an amount of 570.70 g into the reactor at room temperature.
- the scrapped stirrer was stopped and then a pre-emulsion was prepared by dispersing the perfume phase in the aqueous phase with the rotor/stator system. During this step, the temperature was maintained at 10°C. The time and the speed of stirring were adjusted to reach the desired size distribution of the emulsion. Once the emulsion was prepared, the stirring was continued with the scrapped stirrer at 200 rpm till the end of the process.
- the perfume content in the capsules suspension was around 40%, relative to the total weight of the suspension.
- the size distribution of the capsules was controlled by Optical Microscopy and Light Scattering (Mastersizer S, Malvern) while the surface charge was controlled by Zeta potential measurements (Nanosizer, Malvern).
- the synthesis was repeated several times and the value of the Zeta potential measured for the obtained capsules were comprised between +8 and +20 mV, thus indicating that the capsules were cationically charged.
- Polyurea capsules were prepared in a one litre glass double-jacketed reactor equipped with a scrapped stirrer and with an Ystral-rotor/stator system (500-1800 rpm).
- the aqueous stabilizer solution was prepared by dissolving the polyvinyl alcohol (Mowiol ® 18-88, origin: Fluka) and the cationic copolymer Luviquat ® Ultra Care (polyquaternium-44, origin: BASF) in deionised water.
- the final concentration of the polyvinyl alcohol was 0.25% while the concentration of Luviquat ® Ultra Care was 1%, these percentages being relative to the total weight of the stabilizer solution.
- the stabilizer solution was introduced into the reactor at room temperature in an amount of 582.50 g.
- the scrapped stirrer was stopped and then a pre-emulsion was prepared by dispersing the perfume phase in the aqueous phase with the rotor/stator system. During this step, the temperature was maintained at 10°C. The time and the speed of stirring were adjusted to reach the desired size distribution of the emulsion. Once the emulsion was prepared, the stirring was continued with the scrapped stirrer at 200 rpm till the end of the process.
- the perfume content in the capsules suspension was around 28%, relative to the total weight of the suspension.
- the size distribution of the capsules was controlled by Optical Microscopy and Light Scattering (Mastersizer S, Malvern) while the surface charge was controlled by Zeta potential measurements (Nanosizer, Malvern). A positive value of the Zeta potential indicated that the capsules were cationically charged.
- Polyurea capsules were prepared in a one litre glass double-jacketed reactor equipped with a scrapped stirrer and with an Ystral-rotor/stator system (500-1800 rpm).
- the aqueous stabilizer solution was prepared by dissolving the polyvinyl alcohol (Mowiol ® 18-88, origin: Fluka) and the cationic copolymer Luviquat ® Ultra Care (polyquaternium-44, origin: BASF) in deionised water.
- the final concentration of the polyvinyl alcohol was 0.25% while the concentration of Luviquat ® Ultra Care was 1%, these percentages being relative to the total weight of the stabilizer solution.
- the stabilizer solution was introduced in an amount of 570.70 g into the reactor at room temperature.
- the scrapped stirrer was stopped and then a pre-emulsion was prepared by dispersing the perfume phase in the aqueous phase with the rotor/stator system. During this step, the temperature was maintained at 10°C. The time and the speed of stirring were adjusted to reach the desired size distribution of the emulsion. Once the emulsion was prepared, the stirring was continued with the scrapped stirrer at 200 rpm till the end of the process.
- the perfume content in the capsules suspension was around 40%, relative to the total weight of the suspension.
- the size distribution of the capsules was controlled by Optical Microscopy and Light Scattering (Mastersizer S, Malvern) while the surface charge was controlled by Zeta potential measurements (Nanosizer, Malvern). A value of the Zeta potential of +5mV indicated that the capsules were cationically charged.
- Polyurea capsules were prepared in a one litre glass double-jacketed reactor equipped with a scrapped stirrer and with an Ystral-rotor/stator system (500-1800 rpm).
- the aqueous stabilizer solution was prepared by dissolving the polyvinyl alcohol (Mowiol ® 18-88, origin: Fluka) and the cationic copolymer Luviquat ® FC 550 (polyquaternium-16, origin: BASF) in deionised water.
- the final concentration of the polyvinyl alcohol was 0.25% while the concentration of Luviquat ® FC 550 was 0.75%, these percentages being relative to the total weight of the stabilizer solution.
- the stabilizer solution was introduced in an amount of 549 g into the reactor at room temperature.
- the scrapped stirrer was stopped and then a pre-emulsion was prepared by dispersing the perfume phase in the aqueous phase with the rotor/stator system at room temperature. The time and the speed of stirring were adjusted to reach the desired size distribution of the emulsion. Once the emulsion was prepared, the stirring was continued with the scrapped stirrer at 200 rpm till the end of the process.
- the perfume content in the capsules suspension was around 40%, relative to the total weight of the suspension.
- the size distribution of the capsules was controlled by Optical Microscopy and Light Scattering (Mastersizer S, Malvern) while the surface charge was controlled by Zeta potential measurements (Nanosizer, Malvern).
- the synthesis was repeated several times and the value of the Zeta potential measured for the obtained capsules were comprised between +35 and +45 mV, thus indicating that the capsules were cationically charged.
- a perfuming composition was prepared by admixing the ingredients listed in Table 1, in the amounts indicated. The percentages are defined by weight relative to the total weight of the perfuming composition.
- Table 1 Composition of the perfume Ingredients % LogP Steric Hindrance Group 1,8-Cineole 5.00 3.13 1 Verdylate 15.00 3.76 4 ⁇ -Damascone 3.00 4.13 3 Lilial ®1) 12.00 4.36 7 Dihydroterpenyl acetate 6.00 4.42 1 ⁇ -Ionone 2.00 4.42 3 Lorysia ®2) 6.50 4.42 3 Iso E super ®3) 10.00 4.71 4 Cetalox ®4) 2.00 4.76 4 Habanolide ®5) 82.00 4.88 6 1-Methyl-4-(4-methyl-3-pentenyl)-3-cyclohexene-1-carbaldehyde 1.00 5.19 3 Polysantol ®6) 2.00 5.39 2 Patchouli essential oil 3.00 5.5 4 Octalynol 0.
- the logP distribution of the ingredients present in the perfuming composition is summarized in Table 2 and the proportions of the perfuming composition consisting of ingredients from each of high steric hindrance Groups 1 to 7, as described above, is summarized in Table 3. The percentages are defined by weight relative to the total weight of the perfuming composition.
- Table 2 Composition of the perfume by logP of ingredients LogP % logP > 5 10.00 4.5 ⁇ logP ⁇ 5 37.50 4 ⁇ logP ⁇ 4.5 32.50 3.5 ⁇ logP ⁇ 4 15.00 3 ⁇ logP ⁇ 3.5 5.00 Total 100.00
- Table 3 Composition of the perfume by high steric hindrance group High steric hindrance group % Group 1 11.00 Group 2 2.00 Group 3 35.30 Group 4 30.50 Group 5 0.00 Group 6 8.20 Group 7 12.00 Total concentration of ingredients in Groups 1 to 7 99.00 Total concentration of Groups 3, 4, 6 and 7 ingredients 86.00
- This perfuming composition was encapsulated following the process described in Example 2 and added to either a concentrated fabric-softener or a concentrated liquid detergent.
- the concentrated liquid detergent base was a commercially available Tide ® 2x Concentrated HE Free of perfume & dye (trademark of Procter and Gamble, USA).
- the concentrated fabric softener base was prepared by admixing the ingredients listed in Table 4, in the amounts indicated. The percentages are defined by weight relative to the total weight of the unperfumed fabric softener base.
- Table 4 Formulation of the concentrated fabric softener base Ingredient % Stepantex VL90 A Diester Quat 10) 16.50 Proxel GXL 11) 0.04 CaCl 2 (10% aqueous solution) 0.20 Water 83.26 10) Origin:Stepan 11) Origin:Avecia
- Capsules were mixed at 1.25% into the unperfumed softener or liquid detergent and both products were stored for one month in ovens at either 22°C or 37°C before analyzing by GC-MS the amount of perfume having leaked out of the capsules during the month storage.
- Olfactive performance of the microcapsules on dry fabrics when delivered from a consumer product of the softener type
- a perfuming composition as prepared in Example 6 was encapsulated following the process described in Example 2. Capsules were mixed at 1.25% into the unperfumed fabric-softener base described in Example 6. The final concentration of perfume in the softener base was 0.5%. A reference was prepared by mixing at 0.5% the free perfuming composition described in Example 6 with the unperfumed softener base described in the same example.
- the olfactive performance is clearly increased for dry fabrics treated with the encapsulated perfuming composition when compared to those treated with the free perfuming composition.
- the olfactive performance of the towels treated with the softener comprising the encapsulated perfume is already good before rubbing, but the odor intensity is further increased after rubbing, thus showing that release of the perfume from the capsules is enhanced by rubbing the towels.
- a perfuming composition as prepared in Example 6 was encapsulated following the process described in Example 2. Capsules were mixed at 0.75% into the commercially available unperfumed Tide ® 2X HE Free of perfume & dye (trademark of Procter and Gamble, USA) concentrated liquid detergent. The final concentration of perfume in the detergent base is 0.3%. A reference is prepared by mixing at 0.3% the free perfuming composition described in Example 3 with the unperfumed Tide ® 2X HE Free detergent base.
- Example 4 After 1, 3 and 7 days dry, the perfume impact on dry fabrics washed with the encapsulated perfuming composition was perceived stronger than on the dry fabrics washed with the free perfuming composition. As already pointed out in Example 4, the effect is even stronger after rubbing. Indeed, a very significant increase in perfume intensity is observed upon rubbing of fabrics treated with capsules, whereas rubbing has no impact for fabrics washed with the detergent comprising the free perfuming composition.
- a perfuming composition was prepared by admixing the ingredients listed in Table 9, in the amounts indicated. The percentages being defined by weight relative to the total weight of the perfuming composition.
- Table 9 Composition of the perfume Ingredients % LogP Steric Hindrance Group Cyclogalbanate 12) 1.13 2.72 1 Ethyl 2-methyl-pentanoate 13) 1.62 2.76 2,4-Dimethyl-3-cyclohexene-1-carbaldehyde 14) 1.25 2.85 1 Verdyl Acetate 6.25 2.85 4 ⁇ -Undecalactone 1.88 3.06 Yara yara 15) 1.87 3.25 Verdyl propionate 3.75 3.34 4 Dihydroterpineol 0.50 3.42 1 Rose oxide 0.25 3.58 1 Allyl heptanoate 0.63 3.67 Isobornyl acetate 2.50 3.86 5 ⁇ -Damascone 1.00 4.13 3 Terpenyl acetate 7.50 4.34 1 Lilial ® 16) 12.50 4.36 7
- the logP distribution of the ingredients present in the perfuming composition is summarized in Table 10 and the proportions of the perfuming composition consisting of ingredients from each of high steric hindrance Groups 1 to 7, as described above, is summarized in Table 11. The percentages are defined by weight, relative to the total weight of the perfuming composition.
- Table 10 Composition of the perfume by logP of ingredients LogP % logP > 5 5.50 4.5 ⁇ logP ⁇ 5 13.12 4 ⁇ logP ⁇ 4.5 59.75 3.5 ⁇ logP ⁇ 4 3.38 3 ⁇ logP ⁇ 3.5 8.00 2.5 ⁇ logP ⁇ 3 10.25 Total 100.00
- Table 11 Composition of the perfume by high steric hindrance group High steric hindrance group % Group 1 13.13 Group 2 0.00 Group 3 32.25 Group 4 17.50 Group 5 2.50 Group 6 0.62 Group 7 12.50 Total concentration of ingredients in Groups 1 to 7 78.5 Total concentration of Groups 3, 4, 6 and 7 ingredients 62.87
- This perfuming composition was encapsulated following the process described in Example 2 and added to either a concentrated fabric-softener or a concentrated liquid detergent.
- the concentrated liquid detergent base was the commercially available Tide ® 2x Concentrated HE Free of perfume & dye (trademark of Procter and Gamble, USA).
- the concentrated fabric softener base was prepared as in Example 6 Capsules were mixed at 1.25% into the unperfumed softener or liquid detergent and both bases were stored for one month in ovens at either 22°C or 37°C before analyzing by GC-MS the amount of perfume having leaked out of the capsule during the month storage.
- Olfactive performance of the microcapsules on dry fabrics when delivered from a consumer product of the softener type
- a perfuming composition as prepared in Example 9 was encapsulated following the process described in Example 2. Capsules were mixed at 1.25% into the unperfumed softener fabric-softener base described in Example 6. The final concentration of perfume in the softener base was 0.5%. A reference was prepared by mixing at 0.5% the free perfuming composition described in Example 9 with the unperfumed softener base.
- the panel was asked to rate the odor intensity of the towels treated with the fabric softener comprising the capsules, respectively with the fabric softener comprising the free perfume, on a scale from 0 to 7, 0 corresponding to odorless and 7 corresponding to a very strong odor.
- Table 13 Odor intensity of the cotton towels Fresh samples After 1 month 1 day dry 1 day dry Sample Before rubbing After rubbing Before rubbing After rubbing Free perfume 2.0 2.2 1.8 2.0 Encapsulated perfume 3.5 6.8 2.0 5.1
- the olfactive performance is clearly increased for dry fabrics treated with the softener comprising the encapsulated perfuming composition when compared to those treated with the softener comprising the free perfuming composition.
- the olfactive performance of the towels treated with the softener comprising the encapsulated perfume is already good before rubbing, but the odor intensity is further increased after rubbing, thus showing that release of the perfume from the capsules is enhanced by rubbing the towels.
- a clear benefit can still be observed with a fabric softener stored for one month, mostly after rubbing of the fabric.
- a perfuming composition as prepared in Example 9 was encapsulated following the process described in Example 2. Capsules were mixed at 0.75% into the commercially available unperfumed Tide ® 2X HE Free of perfume & dye (trademark of Procter and Gamble, USA) concentrated liquid detergent. The final concentration of perfume in the detergent base was 0.3%. A reference was prepared by mixing at 0.3% the free perfuming composition described in Example 9 with the unperfumed Tide ® 2X HE Free of perfume & dye detergent base.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Fats And Perfumes (AREA)
- Manufacturing Of Micro-Capsules (AREA)
- Cosmetics (AREA)
- Detergent Compositions (AREA)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
IB2008052368 | 2008-06-16 | ||
PCT/IB2009/052414 WO2009153695A1 (en) | 2008-06-16 | 2009-06-08 | Process for preparing polyurea microcapsules |
Publications (2)
Publication Number | Publication Date |
---|---|
EP2300146A1 EP2300146A1 (en) | 2011-03-30 |
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Publication number | Priority date | Publication date | Assignee | Title |
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JP2024500204A (ja) | 2020-12-23 | 2024-01-05 | フイルメニツヒ ソシエテ アノニム | マイクロカプセルを調製するための方法 |
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WO2023275053A1 (en) | 2021-06-30 | 2023-01-05 | Firmenich Sa | Delivery systems |
WO2023006532A1 (en) | 2021-07-28 | 2023-02-02 | Firmenich Sa | Polyamide-based microcapsules |
EP4351772A1 (en) | 2021-07-29 | 2024-04-17 | Firmenich SA | Microcapsules having a mineral layer |
EP4376996A1 (en) | 2021-10-04 | 2024-06-05 | Firmenich SA | Plant protein-based microcapsules |
WO2023078909A1 (en) | 2021-11-03 | 2023-05-11 | Firmenich Sa | Cyclic acetals and ketals for the light-induced release of active aldehydes and ketones |
WO2023111006A1 (en) | 2021-12-14 | 2023-06-22 | Firmenich Sa | Enol ether properfume |
WO2023209139A1 (en) | 2022-04-29 | 2023-11-02 | Firmenich Sa | Musky odorant |
WO2023217589A1 (en) | 2022-05-09 | 2023-11-16 | Firmenich Sa | Polyamide microcapsules |
WO2023217590A1 (en) | 2022-05-09 | 2023-11-16 | Firmenich Sa | Polyamide microcapsules |
WO2024008583A1 (en) | 2022-07-04 | 2024-01-11 | Firmenich Sa | Hybrid microcapsules |
WO2024018014A1 (en) | 2022-07-21 | 2024-01-25 | Firmenich Sa | Composite microcapsules |
WO2024068907A1 (en) | 2022-09-29 | 2024-04-04 | Firmenich Sa | Lily of the valley odorant |
Family Cites Families (30)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5225118A (en) * | 1990-08-15 | 1993-07-06 | Boise Cascade Corporation | Process for manufacturing polyurea microcapsules and product therefrom |
DE19607632A1 (de) * | 1996-02-29 | 1997-09-04 | Bayer Ag | Mikrokapseln mit Wänden aus Umsetzungsprodukten von Biuret-Polyisocyanaten und Guanidinen |
FR2761912B1 (fr) * | 1997-04-14 | 1999-07-02 | Capsulis | Procede destine a faire adherer un produit sur une surface |
FR2801811B1 (fr) * | 1999-12-06 | 2002-05-03 | Gerard Habar | Procede de fabrication de microcapsules portant des charges cationiques |
JP2001202037A (ja) * | 2000-01-20 | 2001-07-27 | Mitsubishi Paper Mills Ltd | 画像表示媒体及びその製造方法 |
ES2253147T3 (es) * | 2000-03-04 | 2006-06-01 | Cognis Ip Management Gmbh | Microcapsulas. |
EP1151789A1 (de) * | 2000-05-03 | 2001-11-07 | Bayer Ag | Mikrokapseln erhältlich unter Verwendung von Eiweisshydrolysaten als Emulgator |
DK1292386T3 (da) * | 2000-06-05 | 2006-03-27 | Syngenta Ltd | Hidtil ukendte mikrokapsler |
DE10117671A1 (de) * | 2001-04-09 | 2002-10-10 | Bayer Ag | Mit duftstoffhaltigen Mikrokapseln ausgerüstetes Leder |
JP2003001100A (ja) * | 2001-06-04 | 2003-01-07 | Microcapsules Technologies | 陽イオン性マイクロカプセルを製造する方法 |
US6620777B2 (en) * | 2001-06-27 | 2003-09-16 | Colgate-Palmolive Co. | Fabric care composition comprising fabric or skin beneficiating ingredient |
CA2512771A1 (en) * | 2003-01-08 | 2004-07-29 | Johnson & Johnson Gmbh | Products comprising a sheet and a wax dispersion |
FR2858766B1 (fr) * | 2003-08-11 | 2005-11-11 | Oreal | Composition cosmetique comprenant des particules metalliques stabilisees, eventuellement enrobees |
WO2005054422A1 (en) | 2003-11-28 | 2005-06-16 | Unilever Plc | Detergent compositions with improved malodour properties and process to make them |
DE102004007312A1 (de) * | 2004-02-14 | 2005-09-01 | Henkel Kgaa | Mikroemulsionen |
US20050226900A1 (en) * | 2004-04-13 | 2005-10-13 | Winton Brooks Clint D | Skin and hair treatment composition and process for using same resulting in controllably-releasable fragrance and/or malodour counteractant evolution |
US20070207174A1 (en) | 2005-05-06 | 2007-09-06 | Pluyter Johan G L | Encapsulated fragrance materials and methods for making same |
US20080206291A1 (en) | 2005-06-30 | 2008-08-28 | Firmenich Sa | Polyurethane and Polyurea Microcapsules |
GB0513803D0 (en) | 2005-07-06 | 2005-08-10 | Unilever Plc | Fabric care composition |
GB0524665D0 (en) | 2005-12-02 | 2006-01-11 | Unilever Plc | Laundry composition |
GB2432850A (en) | 2005-12-02 | 2007-06-06 | Unilever Plc | Polymeric particle comprising perfume and benefit agent, in particular a laundry composition |
GB2432852A (en) | 2005-12-02 | 2007-06-06 | Unilever Plc | Laundry composition including polymer particles containing perfume and a cationic deposition aid |
GB0524659D0 (en) | 2005-12-02 | 2006-01-11 | Unilever Plc | Improvements relating to fabric treatment compositions |
GB2432851A (en) | 2005-12-02 | 2007-06-06 | Unilever Plc | Laundry composition including polymer particles containing perfume and a non-ionic deposition aid |
GB2432843A (en) | 2005-12-02 | 2007-06-06 | Unilever Plc | Perfume carrying polymeric particle |
EP1989283A2 (en) * | 2006-02-28 | 2008-11-12 | The Procter and Gamble Company | Compositions comprising benefit agent containing delivery particles |
JP5629432B2 (ja) * | 2006-04-10 | 2014-11-19 | Jx日鉱日石エネルギー株式会社 | 連続乳化方法およびそのための乳化装置 |
CA2656326A1 (en) | 2006-06-30 | 2008-01-10 | Colgate-Palmolive Company | Cationic polymer stabilized microcapsule composition |
ATE491433T1 (de) | 2006-08-01 | 2011-01-15 | Procter & Gamble | Pflegemittel mit freisetzungspartikel |
EP2094828B1 (en) * | 2006-11-22 | 2013-01-02 | Appleton Papers Inc. | Benefit agent containing delivery particle |
-
2009
- 2009-06-08 EP EP09766232.4A patent/EP2300146B1/en active Active
- 2009-06-08 BR BRPI0915228-8A patent/BRPI0915228B1/pt not_active IP Right Cessation
- 2009-06-08 JP JP2011514157A patent/JP5713892B2/ja active Active
- 2009-06-08 WO PCT/IB2009/052414 patent/WO2009153695A1/en active Application Filing
- 2009-06-08 MX MX2010013244A patent/MX2010013244A/es active IP Right Grant
- 2009-06-08 CN CN200980121385.4A patent/CN102056656B/zh active Active
- 2009-06-08 US US12/993,190 patent/US8426353B2/en active Active
- 2009-06-08 ES ES09766232.4T patent/ES2628202T3/es active Active
-
2010
- 2010-11-30 ZA ZA2010/08586A patent/ZA201008586B/en unknown
Non-Patent Citations (1)
Title |
---|
None * |
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US11034920B2 (en) | 2017-03-24 | 2021-06-15 | Firmenich Sa | Solid scent booster composition |
US11857659B2 (en) | 2017-06-15 | 2024-01-02 | Firmenich Sa | Rinse-off conditioner compositions comprising microcapsules |
US11291969B2 (en) | 2017-06-27 | 2022-04-05 | Firmenich Sa | Process for preparing microcapsules |
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US11491086B2 (en) | 2017-12-14 | 2022-11-08 | Firmenich Sa | Process for releasing an active ingredient |
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CN102056656A (zh) | 2011-05-11 |
CN102056656B (zh) | 2014-01-29 |
BRPI0915228B1 (pt) | 2018-07-10 |
JP5713892B2 (ja) | 2015-05-07 |
ES2628202T3 (es) | 2017-08-02 |
ZA201008586B (en) | 2012-01-25 |
BRPI0915228A2 (pt) | 2017-08-22 |
EP2300146A1 (en) | 2011-03-30 |
JP2011524805A (ja) | 2011-09-08 |
US20110077188A1 (en) | 2011-03-31 |
US8426353B2 (en) | 2013-04-23 |
WO2009153695A1 (en) | 2009-12-23 |
MX2010013244A (es) | 2010-12-21 |
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